CN103979636B - A kind of ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method - Google Patents
A kind of ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method Download PDFInfo
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- CN103979636B CN103979636B CN201410244701.XA CN201410244701A CN103979636B CN 103979636 B CN103979636 B CN 103979636B CN 201410244701 A CN201410244701 A CN 201410244701A CN 103979636 B CN103979636 B CN 103979636B
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Abstract
A kind of ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, it relates to a kind of antibiotic method in degradation of sewage.The present invention is that the treatment process required time in order to solve at present containing antibiotics waste water is longer, and be not suitable for the antibiotic waste water reason of process high density, final product toxicity is large, and parent contaminants cannot thoroughly be degraded, the problem that processing costs is high, energy expenditure is large.Method: will join in cylindricality reactor containing antibiotic waste water, regulates pH, starts ultrasonic generator simultaneously and processes together with ozonizer.The present invention is applied to water treatment field.
Description
Technical field
The present invention relates to a kind of antibiotic method in degradation of sewage.
Background technology
Microbiotic is heavily used in the disease treatment of humans and animals for a long time, and makes an addition in animal-feed with large therapeutic dose, to prevent Animal diseases and to promote its growth.But most microbiotic can not be absorbed by body completely, about there is the microbiotic of 90% to enter in ecotope with original shape or metabolite form via the ight soil of sick humans and animals and urine, through different approaches, soil and water is polluted.At present, a large amount of research reports detecting antibiotic agents about surface water and groundwater has been had in Canada, the U.S., Britain, Germany and the country such as Chinese.Be that a class biological degradation difficulty is large containing antibiotic waste water, in environment, residual quantity is high, the high concentrated organic wastewater that bio-toxicity is strong.In recent years due to the develop rapidly of pharmaceutical industry, particularly antibiotic appearance brings serious pollution to the water resources in the world.Carry out rationally effective improvement to antibiotic waste water extremely urgent, this is the problem being related to the development of society and the following living environment of the mankind.
Current process is a lot of containing the method for antibiotics waste water, and conventional method is biological degradation method, physical method and chemical degradation method.The Chinese patent being CN1101654311 as publication number discloses " a kind of novel method of antibiotic waste water process ", employ up-flow anaerobic sludge blanket-aerobic membrane bioreactor machinery to carry out a biological disposal upon to antibiotic waste water, the hydraulic detention time of Controlling System is 20.5h, COD average removal rate can reach 86.56%, effective clearance of machinery is 80% ~ 85%, but biological degradation method required time is longer, and be not suitable for the process of high density antibiotic waste water, and biological degradation antibiotics waste water also can produce the larger pollutent of toxicity; Pollutent just carries out shifting and accumulating by physical method, it thoroughly can not be degraded; High-level oxidation technology in chemical degradation method comprises ozone oxidation, photochemical catalytic oxidation, wet oxidation, Fenton reagent oxidation, H
2o
2/ UV, O
3/ UV etc., its principal feature produces hydroxyl radical free radical by chemical reaction, pollutent is made effectively to be degraded to carbonic acid gas, water and mineral ion, there is the shortcoming that processing costs is high, energy expenditure is large in chemistry advanced oxidation processes, the method of ozone oxidation wherein comprises antibiotic degraded for organism a lot of in environment, but have not been reported about degrade antibiotic document and patent of ultrasonic ozone United Technologies.
Summary of the invention
The present invention is that the treatment process required time in order to solve at present containing antibiotics waste water is longer, be not suitable for the antibiotic waste water reason of process high density, final product toxicity is large, parent contaminants cannot thoroughly be degraded, the problem that processing costs is high, energy expenditure is large, thus provide a kind of ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method.
Of the present invention a kind of ultrasonic/ozone combined reinforced degradation of sewage in antibiotic method specifically carry out according to the following steps:
To join in cylindricality reactor containing antibiotic waste water, regulate pH to 3 ~ 9, the probe of ultrasonic generator is contained the position of antibiotic waste water liquid level 1/3 from top insertion, start ultrasonic generator simultaneously and process 5min ~ 60min together with ozonizer.
Beneficial effect of the present invention:
One, ultrasonic technique is combined with ozonation technology by the present invention, utilize ultrasonic cavitation effect that ozone molecule is disperseed more, form more poly-hydroxy free radical, thus promote the selective oxidation reaction of ozone and the non-selective oxidation reaction of free radical, improve utilization ratio and the mass-transfer efficiency of ozone, Reaction time shorten, accelerates antibiotic degraded, thus saves running cost; Compared with simple ozone process, of the present invention ultrasonic/the reaction rate constant K of ozone process improves 41%, by augmenting response rate constant, reduces antibiotic transformation period (t
1/2), reach raising speed of reaction, Reaction time shorten, reduce the object of ozone dosage;
Two, use method of the present invention, the COD of waste water also can reach certain clearance, biodegradability (BOD
5/ COD) can be greatly improved, and bio-toxicity also obtains certain alleviation.When reaching 60min when treated, the COD clearance of waste water reaches 80%, BOD
5/ COD increases to 0.54 from 0, and bio-toxicity drops to minimum.
The method of a kind of efficient fast processing antibiotic waste water of the present invention can be used in actual water treatment.
Accompanying drawing explanation
Fig. 1 is degradation curve-time diagram, and curve 1 is the degradation curve-time containing the waste water of sulfamethoxazole in test two, and curve 2 is the degradation curve-time containing the waste water of sulfamethoxazole in test one;
Fig. 2 is speed of reaction-time diagram, and ■ is the data point that test one records, ◆ be the data point that test two records, curve 1 is the speed of reaction-time match curve of test two, and curve 2 is speed of reaction-time match curves of test one;
Fig. 3 is spectrogram, simultaneously curve 1 starts curve of spectrum when ultrasonic generator processes 0min together with ozonizer in test one, simultaneously curve 2 starts curve of spectrum when ultrasonic generator processes 2min together with ozonizer in test one, simultaneously curve 3 starts curve of spectrum when ultrasonic generator processes 5min together with ozonizer in test one, simultaneously curve 4 starts curve of spectrum when ultrasonic generator processes 10min together with ozonizer in test one, simultaneously curve 5 starts curve of spectrum when ultrasonic generator processes 15min together with ozonizer in test one, simultaneously curve 6 starts curve of spectrum when ultrasonic generator processes 30min together with ozonizer in test one, simultaneously curve 7 starts curve of spectrum when ultrasonic generator processes 60min together with ozonizer in test one,
Fig. 4 is COD clearance-time of waste water, biodegradability-time and bio-toxicity-time diagram, and curve 1 is COD clearance-time curve, and curve 2 is bio-toxicity-time diagrams, and Fig. 3 is biodegradability-time curve.
Embodiment
Embodiment one: present embodiment be a kind of ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, specifically carry out according to the following steps:
To join in cylindricality reactor containing antibiotic waste water, regulate pH to 3 ~ 9, the probe of ultrasonic generator is contained the position of antibiotic waste water liquid level 1/3 from top insertion, start ultrasonic generator simultaneously and process 5min ~ 60min together with ozonizer.
The beneficial effect of present embodiment:
One, ultrasonic technique is combined with ozonation technology by present embodiment, utilize ultrasonic cavitation effect that ozone molecule is disperseed more, form more poly-hydroxy free radical, thus promote the selective oxidation reaction of ozone and the non-selective oxidation reaction of free radical, improve utilization ratio and the mass-transfer efficiency of ozone, Reaction time shorten, accelerates antibiotic degraded, thus saves running cost; Compared with simple ozone process, present embodiment ultrasonic/the reaction rate constant K of ozone process improves 41%, by augmenting response rate constant, reduces antibiotic transformation period (t
1/2), reach raising speed of reaction, Reaction time shorten, reduce the object of ozone dosage;
Two, by the method for present embodiment, the COD of waste water also can reach certain clearance, biodegradability (BOD
5/ COD) can be greatly improved, and bio-toxicity also obtains certain alleviation.When reaching 60min when treated, the COD clearance of waste water reaches 80%, BOD
5/ COD increases to 0.54 from 0, and bio-toxicity drops to minimum.
The method of a kind of efficient fast processing antibiotic waste water of present embodiment can be used in actual water treatment.
Embodiment two: present embodiment and embodiment one unlike: the power of ultrasonic generator is 200W ~ 1200W.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the frequency of ultrasonic generator is 20kHz.Other is identical with one of embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: regulate pH be sodium hydroxide and hydrochloric acid.Other is identical with one of embodiment one to three.
Embodiment five: the ozone concn that one of present embodiment and embodiment one to four occur unlike: ozonizer is 2g/h ~ 4g/h.Other is identical with one of embodiment one to four.
Adopt following verification experimental verification effect of the present invention:
Test one: this test be one ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, specifically carry out according to the following steps:
Waste water containing sulfamethoxazole is joined in cylindricality reactor, regulates pH to 9, the probe of ultrasonic generator is contained the position of antibiotic waste water liquid level 1/3 from top insertion, start ultrasonic generator simultaneously and process 60min together with ozonizer; The power of ultrasonic generator is 800W; The frequency of ultrasonic generator is 20kHz; Regulate pH's to be sodium hydroxide and hydrochloric acid; The ozone concn that ozonizer occurs is 4g/h.
Test two: this test is simultaneous test, be adopt independent By Ozone, concrete steps are as follows: join in cylindricality reactor by the waste water containing sulfamethoxazole, regulate pH to 9, start ozonizer process 60min; Regulate pH's to be sodium hydroxide and hydrochloric acid; The ozone concn that ozonizer occurs is 4g/h.
Fig. 1 is degradation curve-time diagram, and curve 1 is the degradation curve-time containing the waste water of sulfamethoxazole in test two, and curve 2 is the degradation curve-time containing the waste water of sulfamethoxazole in test one.As can be seen from the figure, be respectively 95.3% and 87.4% with the method for test one and test two degradation rate when 5min for sulfamethoxazole, the degradation rate that the sulfamethoxazole of two is comparatively tested in test one improves 9%.
Fig. 2 is speed of reaction-time diagram, and ■ is the data point that test one records, ◆ be the data point that test two records, curve 1 is the speed of reaction-time match curve of test two, and curve 2 is speed of reaction-time match curves of test one.The coefficient R of curve 1 and curve 2
20.98917 and 0.96364 respectively, illustrate that two fitting of a curve obtain all fine, the slope of curve 1 and curve 2 and reaction rate constant are 0.3875 and 0.5469 respectively, and illustrate that the speed of reaction of test one is comparatively tested two and improve 41%, antibiotic removal efficiency is higher.
Start to sample respectively when ultrasonic generator processes 0min, 2min, 5min, 10min, 15min, 30min and 60min together with ozonizer in test one simultaneously and carry out ultraviolet-visible spectrum scanning.Fig. 3 is spectrogram, simultaneously curve 1 starts curve of spectrum when ultrasonic generator processes 0min together with ozonizer in test one, simultaneously curve 2 starts curve of spectrum when ultrasonic generator processes 2min together with ozonizer in test one, simultaneously curve 3 starts curve of spectrum when ultrasonic generator processes 5min together with ozonizer in test one, simultaneously curve 4 starts curve of spectrum when ultrasonic generator processes 10min together with ozonizer in test one, simultaneously curve 5 starts curve of spectrum when ultrasonic generator processes 15min together with ozonizer in test one, simultaneously curve 6 starts curve of spectrum when ultrasonic generator processes 30min together with ozonizer in test one, simultaneously curve 7 starts curve of spectrum when ultrasonic generator processes 60min together with ozonizer in test one.Peak corresponding to wavelength 270nm is the charateristic avsorption band of sulfamethoxazole, as can be seen from the figure along with the sulfamethoxazole in the growth waste water in treatment time slowly reduces, almost all disappears when 60min.
Different time sections in test one is extracted to the COD clearance of sample testing waste water, the inhibiting rate of biodegradability and bio-toxicity.Fig. 4 is COD clearance-time of waste water, biodegradability-time and bio-toxicity-time diagram, curve 1 is COD clearance-time curve, curve 2 is bio-toxicity-time diagrams, Fig. 3 is biodegradability-time curve, as can be seen from the figure when reaction proceeds to 60min, COD clearance in waste water can reach 80%, and the biodegradability of waste water brings up to 0.54 from 0, illustrates that the microbiotic in waste water is easily degraded by microorganisms; Before and after process, the bio-toxicity of waste water has had very large change, and when reaction proceeds to 5min, toxicity is maximum, reaches 100%, and along with the carrying out of reaction, bio-toxicity reduces gradually.This illustrates that ultrasonic in combination ozone technology can reduce the bio-toxicity of microbiotic and intermediate product thereof, thus reduces microbiotic potential hazard in the environment.
Claims (4)
1. an antibiotic method in the combined reinforced degradation of sewage of ultrasonic/ozone, is characterized in that in the combined reinforced degradation of sewage of ultrasonic/ozone, antibiotic method is carried out according to the following steps:
To join in cylindricality reactor containing antibiotic waste water, regulate pH to 3 ~ 9, the probe of ultrasonic generator is contained the position of antibiotic waste water liquid level 1/3 from top insertion, start ultrasonic generator simultaneously and process 5min ~ 60min together with ozonizer; The ozone concn that described ozonizer occurs is 2g/h ~ 4g/h.
2. one according to claim 1 ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, it is characterized in that the power of ultrasonic generator is 200W ~ 1200W.
3. one according to claim 1 ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, it is characterized in that the frequency of ultrasonic generator is 20kHz.
4. one according to claim 1 ultrasonic/the combined reinforced degradation of sewage of ozone in antibiotic method, it is characterized in that regulate pH be sodium hydroxide and hydrochloric acid.
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| CN105060643A (en) * | 2015-08-13 | 2015-11-18 | 哈尔滨工业大学 | Antibiotic wastewater treatment device and method for treating antibiotic wastewater by utilizing device |
| CN105502630B (en) * | 2016-02-02 | 2019-03-01 | 博天环境集团股份有限公司 | A kind of processing method of antibiotic production wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102139996A (en) * | 2011-03-23 | 2011-08-03 | 北京沁润泽环保科技有限公司 | Integral treatment process for rural garbage seeping liquid |
| CN102276095A (en) * | 2011-07-14 | 2011-12-14 | 哈尔滨工业大学 | Method for degrading organic pollutants in water by gradient ozone catalytic oxidation |
| CN102285703A (en) * | 2011-06-15 | 2011-12-21 | 南京信息工程大学 | Method for ultrasonic removal of sulfadiazine in water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102139996A (en) * | 2011-03-23 | 2011-08-03 | 北京沁润泽环保科技有限公司 | Integral treatment process for rural garbage seeping liquid |
| CN102285703A (en) * | 2011-06-15 | 2011-12-21 | 南京信息工程大学 | Method for ultrasonic removal of sulfadiazine in water |
| CN102276095A (en) * | 2011-07-14 | 2011-12-14 | 哈尔滨工业大学 | Method for degrading organic pollutants in water by gradient ozone catalytic oxidation |
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